Nanoparticles having metal-containing non-oxide compositions (i.e., “semiconductor” or “quantum dot” nanoparticles) are increasingly being used in numerous emerging applications. Some of these applications include electronics (e.g., transistors and diode lasers), LED displays, photovoltaics (e.g., solar cells), and medical imaging. Quantum dot nanoparticles are also being investigated as powerful new computer processing elements (i.e., qubits). Semiconductor nanoparticles often possess a metal chalcogenide composition, such as CdSe and ZnS.
As a consequence of its small size, the electron band structure of a quantum dot differs significantly from that of the bulk material. In particular, significantly more of the atoms in the quantum dot are on or near the surface, in contrast to the bulk material in which most of the atoms are far enough removed from the surface so that a normal band structure predominates. Thus, the electronic and optical properties of a quantum dot are related to its size. In particular, photoluminescence is size dependent.
Several physical methods are known for synthesizing semiconductor nanoparticles. Some of the physical techniques include advanced epitaxial, ion implantation, and lithographic techniques. The physical techniques are generally useful for producing minute amounts of semiconductor nanoparticles with well-defined (i.e., tailor-made, and typically, uniform) morphological, electronic, magnetic, or photonic characteristics. The physical techniques are typically not useful for synthesizing semiconductor nanoparticles in commercially significant quantities (e.g., grams or kilograms). Several chemical processes are also known for the production of semiconductor nanoparticles. Some of these methods include arrested precipitation in solution, synthesis in structured media, high temperature pyrolysis, and sonochemical methods. For example, cadmium selenide can be synthesized by arrested precipitation in solution by reacting dialkylcadmium (i.e., R2Cd) and trioctyiphosphine selenide (TOPSe) precursors in a solvent at elevated temperatures, i.e.,R2Cd+TOPSe→CdSe+byproducts
High temperature pyrolysis of semiconductor nanoparticles generally entails preparing an aerosol containing a mixture of volatile cadmium and selenium precursors, and then subjecting the aerosol to high temperatures (e.g., by carrying through a furnace) in the presence of an inert gas. Under these conditions, the precursors react to form the semiconductor nanoparticles (e.g., CdSe) and byproducts.
Although the chemical processes described above are generally capable of producing semiconductor nanoparticles in more significant quantities, the processes are generally energy intensive (e.g., by generally requiring heating and a post-annealing step), and hence, costly. Accordingly, commercially significant amounts of the resulting nanoparticles tend to be prohibitively expensive. Furthermore, these processes tend to be significantly limited with respect to control of the physical (e.g., size, shape, and crystalline form) and electronic or photonic characteristics of the resulting nanoparticles.
The microbial synthesis of semiconductor nanoparticles is known, e.g., P. R. Smith, et al., J. Chem. Soc., Faraday Trans., 94(9), 1235-1241 (1998); C. T. Dameron, et al., Nature, 338: 596-7, (1989); and U.S. Application Pub. No. 2010/0330367. However, there are significant obstacles that prevent such microbially-mediated methods from being commercially viable. For example, current microbial methods are generally limited to the production of semiconductor nanoparticles on a research scale, i.e., an amount sufficient for elucidation by analytical methods. In addition, current microbial processes generally produce semiconductor nanoparticles adhered to cell membranes. Accordingly, numerous separation and washing steps are generally needed. Moreover, the range of particle compositions is limited by the reduction potential limitations of microbes as well as the allowable concentration limits of nutritive metal sources before reaching a level of toxicity to the microbes, i.e., “nutrient toxicity”.
Similarly, particles having metal oxide compositions are increasingly being used in numerous emerging applications. Some of these include the use of magnetic nanoparticles (e.g., magnetite) in magnetic refrigeration or magnetic cooling circuits. Ferrite-type nanoparticles, in particular, are being intensely studied for their use in the fields of biomedicine, optics, and electronics. Other applications include photovoltaic materials, as used, for example, in solar cell devices.
Current methods for the production of nanoscale ferrites and other oxide ceramics generally entail calcining a precursor (e.g., a carbonate) at a high temperature, and then mechanical milling the calcined product to reduce the particle size. The process is energy and time intensive, generally difficult to control, and often requires several repetitions of the process before a final product is obtained.
Chemical processes, such as precipitation and sol-gel techniques, are also known for the production of metal oxide particles. However, these processes are typically more expensive than mechanical milling, and also generally highly limited with respect to size or shape control of the resulting particles. Often, a chemical or physical reduction step is needed to convert a metal oxide precursor to a metal oxide product. In addition, these processes often require a mechanical milling step to break up agglomerates formed during the reduction process.
The microbial synthesis of metal oxide nanoparticles is also known. See, for example, U.S. Pat. Nos. 6,444,453 and 7,060,473. However, there are significant problems in the microbial process as currently practiced. For example, there is the difficulty of obtaining pure nanoparticle product bereft of microbial matter. Therefore, numerous lysing or washing steps are often required. There is also the difficulty in controlling the particle size or the morphology of the nanoparticles, as well as limitation in microbial reduction potentials and nutrient toxicity.